Process for treating solid carbonaceous fossil fuels and the products thus prepared

ABSTRACT

Solid carbonaceous fossil fuels such as coal, lignite and peat are treated with an aqueous medium containing a novel catalyst to remove undesirable constituents and produce valuable products. The catalyst is prepared by steps including admixing a water soluble alkali metal silicate with an aqueous medium containing carefully controlled amounts of dissolved water soluble substances which are sources of calcium ion and magnesium ion, reacting the same to produce an aqueous colloidal suspension of the reaction product, admixing a micelle-forming surfactant with the aqueous medium, and agitating the aqueous medium containing the colloidal particles and surfactant to form catalyst-containing micelles. In one variant, combustible sulfur and nitrogen compounds and alkali metal ash are removed, and the resulting treated fuel may be used in urban areas where strict air pollution regulations must be met. The coal, lignite and peat react with water and/or the components thereof when treated with an aqueous medium containing the catalyst, and/or are oxidized or otherwise chemically changed to produce valuable organic chemicals which are soluble in one or more solvents including the aqueous treating medium, water soluble and water insoluble organic extraction solvents, aqueous solutions of organic and inorganic acids and aqueous solutions of organic and inorganic bases.

RELATED APPLICATIONS

This application is a continuation-in-part of copending application Ser.No. 317,097, filed Dec. 20, 1972 now U.S. Pat. No. 3,893,943 on behalfof John W. Willard, Sr. for NOVEL CATALYST AND PROCESS FOR PREPARING THESAME. Application Ser. No. 317,097, in turn, is a continuation ofapplication Ser. No. 108,198 filed Jan. 20, 1971, now abandoned.

THE BACKGROUND OF THE INVENTION

1. The Field of the Invention

This invention broadly relates to an improved process for treating solidfossilized carbonaceous fuels with an aqueous medium in the presence ofa novel catalyst. The invention further relates to the removal ofcombustible sulfur and nitrogen compounds and other undesirableconstituents from solid fossilized fuels, and the solubilization andrecovery of metal and non-metal values therefrom. In one of its morespecific variants, the invention is concerned with the preparation ofsolvent soluble organic compounds and an activated solid carbonaceousresidue from solid fossil fuels. In another variant, the invention isconcerned with the solubilization of solid carbonaceous fossil fuels orcomponents thereof in an aqueous medium containing the aforementionedcatalyst to thereby produce a novel aqueous solution which has highlyunusual and unexpected properties.

2. The Prior Art

Solid fossilized carbonaceous fuels such as coal, lignite and peat areproducts of the gradual decomposition of vegetable matter without freeaccess of air. Bituminous and anthracite coal, and to some extentlignite, are thought to have been formed in the presence of moisture atelevated temperature and pressure. Most authorities believe that coalpasses through successive stages of peat, lignite or brown coal,sub-bituminous and bituminous or soft coal, and anthracite or hard coalunder conditions of increasing temperature and pressure. The carboncontent increases on a weight percent basis as the vegetable matter istransformed from peat into anthracite coal, and much of the carbon iscombined with other elements such as hydrogen, sulfur, nitrogen andalkali metal, alkaline earth metal or heavy metal values.

Solid fossilized carbonaceous fuels and especially coal comprise highmolecular weight three-dimensional cyclic structures which containpredominantly six membered rings. For example, it is known that coalcontains bitumin and humin which have large, flat, aromatic lamellarstructures that differ in molecular weight, degree of aromaticity,oxygen content, nitrogen content and the degree of cross-linking.Volatile matter, fusain, mineral matter, moisture, pyritic sulfur,inorganic sulfates, and organic sulfur and nitrogen compounds also arepresent. Fusain is a mineral charcoal which is consumed during burningin the presence of sufficient oxygen for complete combustion and themineral matter remains behind as ash. Fusain, mineral matter andinorganic sulfates do not contribute to atmospheric pollution uponcomplete combustion of the coal. However, the presence of combustiblesulfur such as pyritic sulfur and organic sulfur compounds results inthe formation of sulfur oxides which, upon reaction with atmosphericmoisture, produce highly corrosive sulfurous acid and/or sulfuric acid.Combustible nitrogen compounds also present similar problems. As aresult, urban areas have strict air pollution regulations which requirethat the sulfur content of solid fossilized carbonaceous fuels bereduced to about 0.5% by weight or less of combustible sulfur so as tocontrol atmospheric pollution.

The prior art processes for reducing the combustible sulfur content ofsolid fossilized carbonaceous fuels are expensive and require elaborateequipment, costly chemicals or vigorous reaction conditions such as hightemperatures and pressures. As a result of the inherent deficiences ofthe prior art desulfurization processes, the coal industry has longsought an efficient low-cost process for removing combustible sulfurfrom coal.

Solid fossilized carbonaceous fuel also has been treated heretofore toproduce organic chemicals, solid carbonaceous products such as coke andactivated carbon, and liquid hydrocarbon fuels. For example, coke isproduced by heating coal at about 1,000°-1,300° F. in a retort. The cokethus produced is a hard porous residium consisting largely of carbonadmixed with mineral ash and other nonvolatile constituents of theoriginal coal. Volatile byproducts are produced such as coal gas, coaltar, coal tar chemicals and ammonia. The low temperature carbonizationof coal at temperatures of about 500°-700° F. produces products whichdiffer substantially from those obtained at the higher carbonizationtemperatures. Nevertheless, both processes involve cracking of the largemolecules of the coal to produce a solid residue consisting largely ofcarbon and mineral ash, and volatile constituents such as coal gas andnormally liquid byproducts.

Liquid and gaseous fuels have been produced from coal by the BergiusProcess. The early Bergius process usually consisted of mixing powderedcoal with heavy tar from previous runs and approximately 5% of ironoxide as a catalyst. The pasty mass thus produced was heated withhydrogen at about 450°-490° F. for around two hours at a pressure ofapproximately 3,000 pounds per square inch. There has been much researchin this area in an effort to produce petroleum-like materials from coal.The more recent processes use different and more effective catalysts andthe reaction mixture is either in liquid or gaseous phase. In all of theprocesses, the coal is subjected to drastic processing conditions.

Activated carbon has been produced heretofore from coal using acombination of high temperature and various chemicals to convert the rawcoal into an activated carbon residue. Some processes involve subjectingfinely divided raw coal to high pressures and temperatures and treatmentin the presence of steam alone or in combination with chemicals. In thelatter process, the pressure is often reduced very quickly causing thesteam that has penetrated the coal particles to expand rapidly. Thisruptures bonds within the coal particles and increases the availablesurface area and porosity.

There are large deposits of solid fossilized carbonaceous materials inthe United States which contain small percentages of valuable metalvalues or non-metal values. Examples of these deposits includeuranium-bearing lignite and coal which are estimated to contain asubstantial percentage of all known uranium reserves discovered to date.Often other valuable metal values are present such as molybdenum,cobalt, zirconium, germanium and the like. Selenium and other valuablenon-metal values also are present in some deposits. Entirelysatisfactory prior art processes were not available heretofore forsolubilizing and recovering these metal values and/or non-metal values.For example, one prior art practice involves burning heavy metal-bearinglignite and recovering the ash which contains the metal values, and thenprocessing the ash into a commercial form of the metal values for salesuch as uranium oxide, vanadium oxide, molybdenum oxide, and the like.In accordance with another prior art practice, the fossil fuel is heatedin a closed system in the presence of hydrogen and under drasticreaction conditions including high temperature and pressure, with orwithout a catalyst, to produce a liquid petroleum-like material and asolid residue which contains the metal values. The residue is separatedfrom the liquid and gaseous products, and is further processed inaccordance with prior art practices to recover the metal values in theform of a marketable commercial product.

All of the processes discussed above which have been used heretofore forconverting solid fossilized carbonaceous fuels into more valuableproducts involve the use of elaborate equipment, numerous processingsteps, large quantities of processing chemicals which are not readilyrecycled, and drastic reaction conditions. As a result, the processesavailable heretofore have been costly to practice and in some instancesuneconomical.

It has also been proposed to use solid carbonaceous fossil fuels asfertilizer, and the presence of fungistatic and bacteriostaticingredients has been suggested. However, entirely satisfactory processeswere not available heretofore to produce acceptable commercial productson a reproducible basis.

THE SUMMARY OF THE INVENTION

The present invention overcomes the aforementioned and still otherdisadvantages of the prior art and provides a novel process forupgrading solid fossilized carbonaceous fuels and producing valuableproducts therefrom. The treating conditions are comparatively mild, andit is not necessary to use unusually high temperatures, pressures,expensive processing chemicals, elaborate apparatus, or other costlyitems.

It is an object of the present invention to provide a novel process forremoving combustible sulfur, nitrogen and other deleterious constituentsfrom solid fossilized carbonaceous fuels.

It is a further object to provide a novel process for treating solidfossilized carbonaceous fuels in an aqueous medium in the pressure of acatalyst to produce valuable solvent soluble organic chemicals and asolvent carbonaceous residue.

It is a further object to prepare a novel char from solid fossilizedcarbonaceous fuels which is useful as an absorbent or adsorbent.

It is a further object to provide a novel process for solubilizing andrecovering valuable metal values or non-metal values from solidfossilized carbonaceous fuels.

It is a further object to provide a novel process for preparing organiccompounds from solid fossilized carbonaceous fuels by destructivedistillation wherein the solid fossilized carbonaceous fuel is treatedin particulate form with an aqueous medium containing a catalyst priorto the destructive distillation step.

It is a further object to provide a novel process for preparing productsuseful in agriculture and animal husbandry from solid fossilizedcarbonaceous fuels.

It is a further object to provide a novel process for solubilizing solidfossilized carbonaceous fuels, or components thereof, and preparing anaqueous solution which has unique biocidal, medicinal and synergisticproperties.

It is a further object to provide a novel products produced by theprocesses of the invention.

Still other objects and advantages of the invention will be apparent tothose skilled in the art upon reference to the following detaileddescription and the examples.

THE DETAILED DESCRIPTION OF THE INVENTION INCLUDING THE PRESENTLYPREFERRED VARIANTS AND EMBODIMENTS THEREOF

In practicing the present invention, a solid carbonaceous fossil fuel inparticulate form is intimately contacted with an aqueous mediumcontaining a catalytically effective amount of a novel catalyst to bedescribed more fully hereinafter. The solid fossil fuel is preferablycoal, lignite, peat or admixtures thereof, and it has active sites whichare capable of reacting with at least one component of the aqueousmedium in the presence of the catalyst. The particles of the fossil fuelare contacted with the aqueous medium under liquid phase conditionsuntil substantially all or a desired proportion of the active sitesreact with the aqueous medium. Thereafter the particles of fossil fuelmay be further treated as will be described more fully hereinafter. Itwill be appreciated that there are certain variants of the inventionwhich produce preferred results and these variants will likewise bediscussed more fully hereinafter.

The fossil fuel need not be pretreated prior to treating with theaqueous medium other than, when desired, crushing or otherwise reducingit to a suitable particle size. The particle size is not critical andmay vary over wide ranges as the aqueous medium has remarkablepenetration properties and is capable of penetrating large lumps. Theparticle size may be, for example, from 1 inch to -300 mesh (Tylerscreen) and preferably is about -10 mesh to -200 mesh, and for manyapplications is from -50 mesh to -100 mesh. It is understood thatparticles as large as 2, 3 or 4 inches, and often mine run fossil fuel,may be treated but longer periods of contact with the aqueous medium maybe necessary to allow sufficient time for adequate penetration andreaction. Also, particle sizes smaller than -300 mesh may be treated butthe expense of grinding the coal to such a fine particle size usuallyoutweighs any advantages that are gained.

The particles of fossil fuel are intimately contacted with the aqueousmedium under liquid phase conditions and in the presence of a sufficientvolume of the aqueous medium to assure that the particles areconveniently and easily contacted therewith. The volume ratio of theaqueous medium to the particles of fossil fuel may vary over wideranges. It is usually preferred that the aqueous medium be present insufficient volume to allow the particles to be easily agitated thereinsuch as by means of a prior art stirring or agitating device.

The concentration of the catalyst in the aqueous medium also may varyover a wide range as it is only necessary that a catalytic amount bepresent. Suitable catalyst concentrations are discussed more fullyhereinafter. For example, the concentrated catalyst solution as producedby Example I may be diluted with approximately 30- 1000 volumes of waterand for better results in some instances with about 100-200 volumes ofwater to thereby arrive at a satisfactory aqueous treating medium.

The pH value of the aqueous treating medium also may vary over wideranges such as from about 1 to 13.5. The initial pH value is preferablygreater than 7, and is usually about 8-11. There is a tendency for thepH value to decrease as the reaction proceeds. If desired, the pH valueof the aqueous medium may be adjusted as the reaction proceeds byaddition of a base such as alkali metal hydroxide to thereby partiallyor fully restore the initial pH value, but this is not essential.

The temperature of treatment may likewise vary over wide ranges and maybe, for example, between the freezing point and the boiling point of theaqueous medium under the existing pressure conditions. Usuallyatmospheric pressure is preferred, and in such instances, the aqueousmedium may have a temperature of approximately 0° C. to 100° C. and isoften about 20°-60° C. Surprisingly, lower temperatures of treatmentsuch as 0°-10° C. appear to enhance the rate and degree of oxidation andthus lower temperatures may be preferred in instances where a maximumamount of oxidation is desired. Higher temperatures than 100° C. may beemployed under superatmospheric pressure.

For example, provided that the pressure is sufficient under the existingtemperature to maintain liquid phase conditions, the temperature may be100°-200° C. or higher. Nevertheless, such extreme reaction conditionsare not necessary and are usually avoided.

Inexpensive reaction vessels or open vats, with or without agitators andother simple auxiliary equipment, are satisfactory and may be used withgood results. The period of treatment may be varied over wide ranges. Itis only necessary that the aqueous medium be intimately contacted withthe fossil fuel particles for a period of time sufficient for thereaction to occur and continued treatment is not deleterious. Theminimum period of treatment will vary to some extent with the remainingconditions, such as the particle size of the fossil fuel, theconcentration of the catalyst, the pH value of the aqueous medium andthe reaction temperature. The period of treatment may vary, for example,from approximately 5 minutes or less to 24 hours or more but it isusually from about 15 minutes to 2 hours. As a general rule, the amountof oxidation increases with time provided all of the remainingconditions of treatment remain the same.

Solid carbonaceous fossil fuels such as coal, lignite and peat haveactive carbon atoms or active sites. Examples of the active sitesinclude carbon-to-carbon double or triple bonds, carbon-to-oxygen bond,carbon-to-sulfur bonds, carbon-to-nitrogen bonds, carbon-to-metal bonds,carbon attached to an electronegative group, and carbon bonded orotherwise attached or attracted to a dissimilar substrate which is acomponent of the fossil fuel. The catalyst of the present inventioncauses the liquid water in the aqueous treating medium to exhibit veryunusual and heretofore unrecognized properties in the presence of fossilfuels having the aforementioned active carbon atoms or active sites.While the exact nature of the reaction is not known at the present time,it appears that water or some component of water reacts with or altersthe active carbon atoms or active sites to thereby produce pronouncedchemical and/or physical changes. For example, the fossil fuel may beoxidized to produce useful organic oxidation products such as carboxylicacids and hydroxycarboxylic acids. It is also possible to fix nitrogenin the form of organic compounds by treating the fossil fuel in thepresence of an atmosphere containing elemental nitrogen. Additionally,combustable sulfur, nitrogen, and other deleterious substances arealtered to permit their removal by prior art techniques such as byextraction in the aqueous treating medium or with solvents subsequent tothe treatment. Additionally, metal values present in the fossil fuel aresolubilized or rendered soluble upon extraction with solvents therebyallowing the metal values to be concentrated and recovered. The treatedparticles also have a much higher water content than before treatment.The aqueous treating medium following treatment contains the watersoluble constituents of the treated fossil fuel particles.

The treated particles also undergo physical changes as well as chemicalchanges. For example, certain chemical or physical bonds existing withinthe particles are broken upon treatment with the aqueous medium. Theresultant treated fossil fuel may be crushed, ground or otherwisereduced to a more finely divided form with little effort. It is alsopossible to easily separate and remove noncarbonaceous material such asmineral matter from the particles and thereby further reduce theconcentration of undesirable sulfur and nitrogen compounds andash-forming constituents. In instances where the fossil fuel is acarbonaceous are containing valuable metal values, the treatment in theaqueous medium solubilizes or otherwise renders the metal values moresusceptible to solvent extraction and concentration by prior arthydrometallurgical techniques.

When the aqueous medium containing the novel catalyst is contacted withthe fossil fuel, there is a period of activation during which there islittle or no reaction. This activation period may be eliminated orreduced markedly by pre-treating the fresh catalyst suspension with asmall portion of the fossil fuel, or by using a recycled catalystsolution from a previous treatment. In a preferred variant, all or partof the aqueous catalyst suspension is recycled so that an activatedcatalyst is always available for contacting with fresh portions of thefossil fuel. The activated aqueous catalyst suspension thus produced ismuch more effective and has properties which differ substantially fromthose of the initially prepared catalyst.

The aqueous treating medium containing the water soluble constituents ofthe treated fossil fuel is separated from the particles. When desired,all or a portion of the separated treating medium may be recycled andused to treat additional fossil fuel as aformentioned. The resultanttreated particles are changed in appearance and acquire the physicalappearance and properties of weathered (oxidized) fossil fuels such asLeonardite. The separated particles may be washed with water and thenextracted with various solvents to recover organic compounds and otherdesired constituents therefrom. The soluble constituents in the aqueousmedium may be recovered therefrom by precipitation, such as byprecipitation with a mineral acid, or other techniques may be employedsuch as by evaporating the water and precipitating the desiredconstituents from the concentrated liquor.

The treated particles contain large amounts of water and the excesswater and organic compounds may be removed therefrom simultaneously byextracting with a water soluble organic solvent. Examples of suitablewater soluble organic solvents include the water soluble alcohols andespecially those containing about 1-4 carbon atoms, the water solubleketones and especially those containing about 1-4 carbon atoms, watersoluble polyhydroxy compounds such as the glycols, and other similarwater soluble organic solvents. The treated fossil fuel is intimatelycontacted with the water soluble organic solvent under liquid phaseconditions. The temperature of extraction may vary between the freezingpoint and the boiling point of the solvent, but is preferably about roomtemperature or at a moderately elevated temperature. This extractionusually removes most of the absorbed water and organic compounds. Ininstances where the extracted fossil fuel contains organic compoundswhich are not soluble in the organic solvent, then they may be extractedwith a water insoluble organic solvent such as normally liquidhydrocarbons and especially those containing about 5-12 carbon atoms,normally liquid halogenated hydrocarbons and especially those containingabout 4-8 carbon atoms, and normally liquid fractions derived frompetroleum such as petroleum ether, gasoline, kerosene, gas oil, anddiesel fuel. This second extraction with the water insoluble organicsolvent is likewise carried out under liquid phase conditions and attemperatures between the freezing point and boiling point of the solventunder the existing pressure, and preferably at approximately roomtemperature or at a moderately elevated temperature.

The resultant extracted solid fossil fuel residue is substantially freeof organic compounds produced by the treatment but contains inorganiccompounds which may be removed by extraction. The extracted residue isseparated from the organic solvent and the inorganic compounds may berecovered therefrom by extraction with water soluble bases and/or acids.The extracted organic compounds may be separated from the aforementionedwater insoluble organic solvents by distillation or fractionation. It isusually desirable to acidify the organic solvent-water solution beforedistillation. It is possible to separate the extracted organic compoundsfrom the water soluble organic solvent by agitating with a waterinsoluble solvent as aforementioned. When this is done, some of theextracted organic compounds dissolve in the water insoluble organicsolvent and form one layer. Another layer of extracted organic compoundsseparates as a semi-solid layer, and the water content of the extractionmixture separates as a third layer. The water layer may be drawn off anddiscarded, and the upper two layers may be separated individually or asa mixture from which the water insoluble solvent is separated bydistillation or fractionation. The resultant organic compounds or coalchemicals are valuable raw materials for the production of prior artorganic compounds.

The organic solvent extracted residue may be further extracted with anaqueous acidic solution of an organic and/or inorganic acid. Examples ofwater soluble acids include hydrochloric acid, nitric acid, sulfuricacid, phosphoric acid and water soluble organic acids such as formicacid, acetic acid, propionic acid, and trichloroacetic acid. Extractionwith the aqueous acid results in the removal of compounds containingmetal values and other inorganic constituents. In instances where thetreated fossil fuel contains metal values or non-metal values such asuranium, cobalt, vanadium, molybdenum, zirconium, germanium or selenium,then surprisingly the desired values may be solubilized and recovered byprior art hydrometallurgical techniques. The treatment of the fossilfuel with the catalyst suspension alters the metal and non-metal valuesand renders them amenable to solubilization and extraction in the acidicleach solution whereas prior to the treatment, the metal values can notbe easily solubilized and extracted.

The organic solvent extracted residue also may be further extracted withan aqueous base. Examples of water soluble bases which may be usedinclude sodium hydroxide, potassium hydroxide and ammonium hydroxide.The aqueous solution of the base may be intimately contacted with thefossil fuel residue and any amphoteric metal values and solublenon-metal values may be removed, or other soluble inorganicconstituents. The extraction step with the aqueous base may eitherprecede or follow the extraction step with the acidic solution dependingupon the substances to be removed. As was true of the acid extractionstep, valuable metal or non-metal values may be recovered from the leachsolution following prior art hydrometallurgical techniques.

The resultant extracted fossil fuel residue now has the desirableproperties of activated charcoal or activated carbon. For example, theextracted residue may be used to absorb acidic gases such as hydrogenchloride, hydrogen fluoride, hydrogen bromide, hydrogen sulfide, sulfurdioxide, sulfur trioxide, carbon dioxide and halogens includingchlorine, fluorine, and bromine. The acidic gases may be absorbed bypassing a gaseous stream containing the substance to be absorbed througha contained body of the extracted fossil fuel residue following atechnique analogous to that employed with activated carbon or activatedcharcoal. When the fossil fuel residue has reached its absorptioncapacity, it may be regenerated and thereafter reused by intimatelycontacting it with an aqueous solution of a base such as aqueous sodiumhydroxide, potassium hydroxide, or ammonium hydroxide. This is aconvenient method of preparing salts of the acidic substance andespecially hypohalite salts.

The extracted fossil fuel residue is also capable of absorbing largequantities of normally liquid hydrocarbons. Thus, the extractedparticles may be used to absorb petroleum or liquid fractions derivedtherefrom and thereby control oil spills. The extracted particles arelighter than water, and in instances where the oil is present in theform of an oil slick floating on the water, the floating extractedparticles are in intimate contact therewith and absorb the oil. Theresultant solid residue and the absorbed oil content may be easilyseparated from the water by skimming, filtration or other suitableseparation process.

In a further variant of the invention, the fossil fuel is treated withan oxidizing agent before, during or following treatment with theaqueous medium containing the catalyst to thereby aid in solubilizingadditional organic compounds. The oxidizing agent may be air, elementaloxygen, ozone, peroxides such as hydrogen peroxide or the alkali metalperoxides, or other suitable oxidizing agents. The fossil fuel isreacted with the oxidizing agent in an amount to partially oxidize orartificially weather it without combustion. For example, air orelemental oxygen may be bubbled through the aqueous medium while incontact with the fossil fuel, or the fossil fuel may be intimatelycontacted with air or elemental oxygen at elevated temperature prior totreatment with the aqueous medium. Also, the extracted fossil fuelparticles from which the organic and/or inorganic constituents have beenremoved may be partially oxidized by intimately contacting the same withan oxidant to produce additional oxygenated organic compounds. Theoxygenated organic compounds thus produced may be recovered by theafore-mentioned extraction steps.

In a further variant of the invention, the extracted fossil fuel issubjected to destructive distillation to produce organic compounds. Theresultant organic compounds are not the same as are produced whendestructively distilling the original fossil fuel. Thus, the treatmentof the fossil fuel alters the chemical composition and allows noveldestructive distillation products to be produced.

The treated fossil fuel is also useful in the preparation of a syntheticfertilizer. The fertilizer may be prepared by adding to the treatedfossil fuel a phosphate-containing compound such as phosphoric acid orthe alkaline earth metal salts thereof, a nitrogen containing compoundsuch as ammonia, amonium salts or nitrates, and a potassium-containingcompound such as potassium chloride. This is preferably done while thetreated fossil fuel is wetted with the aqueous treating medium. Theresultant fertilizer has trace elements and humus contained in thefossil fuel in addition to the added phosphorous, nitrogen and potashand it is remarkably effective. Lignite, and especially weatheredlignite such as Leonardite, is especially useful in preparingfertilizers.

The extracted fossil fuel is substantially free of deleteriouspollutants such as combustible sulfur and nitrogen compounds and it maybe used as a premium fuel. Very little of the heat value is lost and itmay be burned in coal-burning furnaces in a manner analogous to coal.The treated fossil fuel may be pelletized if desired prior to burning.The combustion gases are substantially free of sulfur dioxide ortrioxide and thus the fuel meets strict standards in this respect. Ininstances where the treated fossil fuel is used for firing boilers, thetube life is increased very markedly due to the absence of corrosivecontaminating substances which tend to shorten tube life.

The oxidation of the fossil fuel and the formation of acidic organiccompounds may be enhanced by treating with the aqueous catalystsuspension at temperatures approaching the freezing point, such as about0°-10° C. and preferably about 0°-4° C. The degree of oxidation is alsocontrolled to some extent by the materials used in constructing thereaction vessel and the materials of construction of auxiliary apparatusin contact therewith such as agitators. Surprisingly, constructing theequipment from nonconductors of electricity such as polyolefins resultsin a maximum degree of oxidation under a given set of operatingconditions. Constructing the equipment from good conductors ofelectricity such as steel and other metals results in a minimum degreeof oxidation for a given set of treating conditions, whereasconstructing the equipment from glass or ceramic materials results in anintermediate degree of oxidation. The reason for this unusual phenomenonis not fully understood at the present time but it is obvious that thethree products differ markedly. Thus, the process of the presentinvention is capable of controlling the level of oxidation under a givenset of reaction conditions.

It is not always necessary nor desirable to separate the catalystsuspension from the treated fossil fuel. For example, in some instancesit is advantageous to evaporate the water content of the aqueoussuspension, either at atmospheric pressure or preferably under reducedpressure, to thereby deposit the catalyst micelles on the treated fossilfuel particles. When this is done, addition of water thereto reactivatesthe catalyst micelles and the particles are subjected to a furthertreatment with the aqueous catalyst suspension. This variant isespecially advantageous in instances where it is desired to prepare thesolution of the treated fossil fuel to be described hereinafter.

In a further variant of the invention, the solid particles of thetreated fossil fuel, or components thereof, are further treated andsolubilized in the aqueous catalyst suspension to produce a novelaqueous solution which has highly unusual and unexpected properties. Theterm "solution" as used herein when referring to this product isintended to embrace finely divided suspended substances which are not intrue solution. The resulting solution has, for example, uniquegermicidal, medicinal, and synergistic properties, and it also hasimportant applications in agriculture and animal husbandry.Additionally, the resultant solution may be used in practicing theapplicant's invention disclosed and claimed in U.S. Pats. No. 3,864,475and 3,874,917, and copending U.S. patent applications Ser. No. 388,774,389,541, 455,022, 389,542, and 455,021. The disclosures of these patentsand pending applications are incorporated herein by reference. It isunderstood that the fossil fuel solutions described hereinafter, whichcontain the novel catalyst suspension of the invention as an ingredient,may be substituted for the aqueous catalyst suspension per se which isused in the aforementioned United States Patents and pending UnitedStates applications. It is only necessary to substitute a like amount ofthe solution of this invention for the aqueous catalyst suspension ofthe prior inventions based upon the weight of the catalyst present ineach instance.

The fossil fuel solutions described hereinafter may be prepared fromcoal, lignite or peat. However, the solutions prepared from ligniteproduce superior results and thus are presently preferred. Accordingly,the discussion appearing hereinafter may be directed specifically to theuse of lignite but it is understood that the invention is notnecessarily limited thereto.

The lignite is first treated with the aqueous catalyst suspensionfollowing the aforementioned general procedure to produce a catalysttreated lignite product. It is usually preferred that the aqueouscatalyst suspension be evaporated, preferably under vacuum, to therebydeposit the catalyst micelles on the lignite particles and produce a drytreated lignite product for subsequent use. In such instances, it isonly necessary to add water to reactivate the catalyst micelles andthereby further treat the lignite particles. In instances where thecatalyst suspension was removed from the treated particles, then it isnecessary to further treat the lignite particles with additionalcatalyst suspension. It is also usually preferred to use a concentratedcatalyst suspension, such as that produced in Example I prior todilution. The catalyst suspension used in the further treatment eithercontains sufficient alkali metal base to form water soluble salts of theorganic acids that are produced, or additional alkali metal hydroxidemay be added for this purpose. Ammonium hydroxide also may be used.Additionally, in instances where the lignite initially treated has notbeen oxidized or weathered, it is usually preferred to add an oxidizingagent at some stage of the treating process. This may be during thefirst treatment of the lignite, or it may be during a subsequenttreatment with the aqueous catalyst suspension. Also, the treatedlignite particles may be extracted with organic solvents and/or aqueoussolutions of acids or bases prior to solubilization. Regardless, of thespecific procedure which is followed, the lignite particles are treatedwith the aqueous catalyst suspension in the presence of sufficient basesuch as alkali metal hydroxide and/or ammonium hydroxide to result inthe formation of humin salts or other organic acid salts.

The concentrations of the catalyst suspension and the dissolved solidsin the solution may vary over extremely wide ranges. In a number ofinstances, the concentrations thereof are determined to some extent bythe end use of the solution. Some uses require very dilute solutions,whereas other uses require much more concentrated solutions. Also, it isoften advantageous to market a concentrated solution which is diluted bythe customer at the time of use to save packaging and shipping costs. Asa general rule, the concentration of catalyst solids in the solution iswithin the ranges aforementioned for the aqueous treating medium. Theconcentration of dissolved lignite in the solution may be from about 0.1part per million to about 10% by weight, or higher. Solutions containingat least 500 parts per million of dissolved lignite, and preferablyabout 600-700 parts per million or more exhibit pronouncedbacteriostatic and/or fungistatic properties. Solutions for general usein agriculture and animal husbandry need contain only about 0.5-100parts per million of dissolved lignite, although more concentratedsolutions may be provided initially for dilution. As a general rule, thesolutions usually contain 1% or less of dissolved lignite.

The solutions of the solid carbonaceous fossil fuel are useful in anumber of diverse fields. This is thought to be due in part to thepresence of trace elements and organic compounds used by the growingvegetation which was the precursor of the coal, lignite and peat. Thetreatment of the fossil fuel with the aqueous catalyst alters thestructure thereof and liberates and makes available the trace elementsand other substances contained therein. The solution contains substanceswhich have properties characteristic of bacteriocides and fungicides andwhich are capable of protecting seeds, plants during their growth, andanimals consuming the plants. Other useful substances also are presentsuch as bio-regulators which control the rate of growth and especiallygrowth accelerators, and substances which enhance the resistance of theplants to adverse conditions of growth or stress such as freezing,drought, physical damage to foilage and transplanting.

The solutions of the fossil fuel have the following uses in agriculture:

1. Soil treated with a dilute aqueous solution of the solubilized fossilfuel is markedly more fertile than untreated soil and the increase infertility cannot be attributed to the plant food content of thesolution. It appears that formerly unavailable nutrients in the treatedsoil become available for use by growing plants following treatment withthe solution. This increases the effective concentration of availablenutrients in the soil and thereby increases the fertility and promotesthe growth of plants.

2. Addition of the solution to the soil appears to cause the soil toattract and hold moisture. Laboratory tests prove that temperatures ashigh as 350° F. are necessary to remove all of the water from thetreated soil. The water is retained at temperatures far in excess of theboiling point.

3. The solubilized lignite is largely in the form of salts of humic acidand other carboxylic acids. Treatment of soil with the solution thusadds humus and the other aforementioned desirable substances.

4. Seeds sprayed with the lignite solution when in the seed bed sproutfaster and have a higher germination rate than untreated seeds. Theseedlings also have a very rapid growth rate and may be transplantedearlier.

5. Cuttings placed in a dilute solution of lignite form sufficient rootsfor transplanting much more rapidly than the same cuttings placed inuntreated water.

6. Plants treated with the lignite solution withstand drought betterthan untreated plants.

7. Plants treated with the lignite solution grow much larger thanuntreated plants, and the quality of the produce is as good or betterthan that from untreated plants or seeds.

8. Plants such as potatoes sprayed with the lignite solution recoverfaster after a hard freeze than do untreated plants. Crops such aspotatoes may be planted much earlier in the Spring and in some instanceseven in the Fall.

The lignite solution is also useful in the storage of crops. Lignitesolutions sprayed on corn in non-airtight storage having a moisturecontent of 25% eliminate mold and rot. The treated corn also has a sweetsilage-like odor and samples show the protein content increased from 9%to 12% due to the growth thereon of a protein-yielding yeast. There wasalso some evidence of an increase in sugar content. Cubes formed fromnew mown hay and treated with the lignite solution did not spoil whenexposed to the elements whereas untreated cubes did spoil. Grain andforage appears to be more palatable and digestible when sprayed with thelignite solution than when untreated. Tests with a fungi inperfectigrown on ligno-cellulose treated with the lignite solution showed thatprotein is produced at low cost which is suitable for use as animalfeed.

The catalyst treated fossil fuels, and especially catalyst treatedlignite, are useful as animal feed supplements. The fossil fuelsolutions also may be similarly used. It is only necessary to add thetreated fossil fuel or solution to the standard feed mixture in anamount of, for example, approximately 1-10% and preferably approximately5%. Animals eating the feed grow faster and with less disease thananimals fed untreated feed.

The lignite solution has medicinal and synergistic properties whichrender it useful in animal husbandry applications. For example, it maybe synergistically combined with antibiotics in the treatment offoot-rot in sheep and cattle and pink eye or cancer eye in cattle. It isalso useful in relieving stress and infection in weaning calves andpigs, in the treatment of burns, cuts, bruises, and sprains, in thetreatment of ketosis in sheep.

The preparation of the novel catalyst used in practicing the presentinvention is described hereinafter.

PREPARATION OF THE CATALYST

The catalyst used in practicing the present invention may be prepared asdescribed below. In the presently preferred process for preparing anaqueous suspension of the catalyst, a water soluble alkali metalsilicate is admixed and reacted with an aqueous solution of a watersoluble dissolved substance which is a source of calcium ion and a watersoluble dissolved substance which is a source of magnesium ion toproduce a finely divided or colloidal suspension of the reactionproduct. The aqueous solution contains the dissolved substancesinitially in amounts to provide between about 1 × 10⁻⁴ and 1 × 10⁻¹ moleper liter each of calcium ion and magnesium ion, preferably betweenabout 1 × 10⁻³ and 1 × 10⁻² mole per liter, and for still better resultsbetween 1 × 10⁻³ and 6 × 10⁻³ mole per liter. The dissolved substancesshould also be present in amounts to provide a molar ratio of calciumion to magnesium ion between about 2.0:1.0 and 1.0:2.0, and preferablyabout 1.5:1.0 and 1.0:1.5. For best results, the aqueous medium shouldcontain the dissolved substances in amounts to provide between about 2.5× 10⁻³ and 3.0 × 10⁻³ mole per liter each of calcium ion and magnesiumion, and the molar ratio of calcium ion to magnesium ion should be about1.0:1.0, e. g., 2.9 × 10⁻³ mole per liter of calcium ion and 2.7 × 10⁻³mole per liter of magnesium ion. The alkali metal silicate should havean alkali metal oxide to silicon dioxide ratio between about 0.9:1.0 andless than 2.0:1.0, and preferably between about 0.9:1.0 and 1.2:1.0. Thealkali metal silicate should be admixed with the aqueous medium in anamount of about 0.05-2 moles per liter, preferably about 0.1-1 mole perliter, and for still better results about 0.2-0.5 mole per liter. Forbest results, the alkali metal silicate should be an alkali metalmeta-silicate having an alkali metal oxide to silicon dioxide ratio ofabout 1:1, and it should be admixed with the aqueous medium in an amountto provide about 0.2-0.3 mole per liter, e.g., about 0.25 mole perliter.

Examples of sources of calcium ion and magnesium ion for use inpreparing the aqueous solution include mineral acid salts such as thehalides, sulfates, bisulfates, nitrites, and nitrates of calcium andmagnesium. The chlorides are usually the preferred halides, and bothcalcium and magnesium chloride are soluble and may be used. Magnesiumsulfate and bisulfate are soluble and often are the preferred sources ofmagnesium ion. Calcium sulfate is only slightly soluble in water andusually is not a preferred source of calcium ion, but calcium bisulfateis somewhat more soluble. While calcium and magnesium nitrite or nitrateare soluble in water and may be used, these substances are not preferredin most instances. The sources of calcium ion and magnesium ion aredissolved in the aqueous medium in amounts to provide calcium ion andmagnesium ion within the above ranges. Complete ionization is assumedwhen calculating the quantities to be dissolved and any desired order ofaddition is satisfactory. For example, the source of calcium ion may beadded to the aqueous medium before, during or after the source ofmagnesium ion.

The alkali metal silicate to be admixed with the aqueous medium ispreferably a water soluble sodium or potassium silicate having an alkalimetal oxide (M₂ O) to silicon dioxide (SiO₂) mole ratio between about0.9:1.0 and less than 2.0:1.0, and preferably between about 0.9:1.0 and1.2:1.0. The best results are usually obtained with an alkali metalmetasilicate having an alkali metal oxide to silicon dioxide ratio ofabout 1:1. Hydrated alkali metal silicates dissolve faster and should beused for best results when the alkali metal silicate is added in solidform. In instances where an anhydrous alkali metal silicate is used, itmay be desirable to dissolve it in water and then add the solution tothe aqueous medium. Sodium metasilicate is preferred and usually ahydrated sodium metasilicate such as the pentahydrate gives the bestresults.

Carbonate ion and/or bicarbonate ion should not be present in theaqueous medium in substantial concentrations as the calcium ion andmagnesium ion are precipitated in the form of their respectivecarbonates. The free carbonate ion and/or bicarbonate ion concentrationsin the aqueous medium should not exceed about 10 parts per million byweight based upon the combined weight of the water and the ingredientsadded thereto and for this reason, the alkali metal silicates should besubstantially free of carbonate ion and bicarbonate ion. A small amountof precipitated calcium carbonate and/or magnesium carbonate may bepresent in the aqueous medium provided additional calcium ion andmagnesium ion are available to meet the above defined concentrations.

Distilled water and/or deionized water are usually preferred over anatural or untreated water when preparing the aqueous medium. Ininstances where water is used which contains substantial initialconcentrations of alkaline earth metal ions, then this should be takeninto consideration in calculating the amounts of the sources of calciumion and magnesium ion which are necessary to arrive at the finalconcentrations previously discussed.

An electrolyte which aids in the preparation of colloidal suspensionsmay be present in the aqueous medium at the time of admixing the alkalimetal silicate therewith. Examples of electrolytes include those used inpreparing prior art colloidal suspensions such as the alkali metalhalides, sulfates and bisulfates. Sodium chloride, sodium sulfate andsodium bisulfate are usually preferred. The electrolyte should be addedin small amounts such as, for example, about 0.00001-0.1 mole per liter,but often larger or smaller amounts may be present.

The conditions under which the alkali metal silicate is admixed with theaqueous medium and reacted with the sources of calcium ion and magnesiumion are not critical provided the reaction mixture is maintained in theliquid phase. The reaction temperature may be, for example, between thefreezing point and boiling point of water under the existing pressureconditions. At atmospheric pressure, the temperature is usually about10°-90° C and often a more convenient temperature is about 20°-50° C. Inmany instances, ambient or normal room temperature is satisfactory.

The degree of agitation is not critical, and mild to vigorous agitationmay be employed during addition of the alkali metal silicate. For thebest results, the aqueous medium should be agitated sufficiently toassure rapid and uniform admixing of the alkali metal silicate. Aftercompleting the addition of the alkali metal silicate, when desired theagitation may be continued for a sufficient period of time to assurecomplete reaction and aging of the resulting colloidal suspension, suchas for approximately 1-5 minutes to one hour or longer.

Upon admixing the alkali metal silicate with the aqueous medium, ittakes on a turbid appearance but in most instances no significant amountof visible precipitate is formed. The colloidal suspension of thereaction product thus produced should be strongly basic and may have apH value of, for example, approximately 10-14 and preferably about11-13, and for best results about 12. In view of this, the initial pHvalue of the aqueous medium containing the dissolved sources of calciumion and magnesium ion is of importance and should be about 6-9 andpreferably about 7-8. When necessary, it is possible to adjust the pHvalue of the aqueous medium to the foregoing levels either before duringor after addition of the alkali metal silicate by adding bases such assodium or potassium hydroxide, or mineral acids such as sulfuric orhydrochloric acid.

The colloidal suspension may be stored for several weeks or longer whileawaiting the further treatment described hereinafter. In instances wherethe colloidal suspension is to be stored over a substantial period oftime, the pH value should be maintained at the above described level andthe storage vessel is preferably a tightly capped polyethylene bottle orother inert plastic container which prevents the contents from absorbingcarbon dioxide from the atmosphere.

The colloidal suspension of the reaction product is not suitable for useas a catalyst as prepared and it should be agitated sufficiently in thepresence of a micelle-forming surfactant to form catalyst-containingmicelles. The degree of agitation, the length of the agitation period,and the amount of the micelle-forming surfactant that is present in thecolloidal suspension are controlled at levels favorable to the formationof micelles. For example, the surfactant may be present in an amount ofabout 0.001-0.1 mole per liter and preferably about 0.03-0.07 mole perliter for most surfactants. Smaller or larger amounts may be effectivewith some surfactants such as 0.0001 mole per liter or less, or 0.2 moleper liter or more. About 0.05 mole per liter often gives the bestresults with many surfactants.

The minimum period of agitation and the minimum degree of agitation thatare required for micelle formation varies somewhat with temperature andthe type and amount of surfactant. As is well understood in this art,gradually increasing these variants in the presence of an effectiveamount of the micelle-forming surfactant will result in micelleformation when the proper levels are reached. As a general rule, longerperiods of agitation and/or more vigorous agitation are required to formmicelles at lower temperatures approaching the freezing point of thecolloidal suspension than at higher temperatures approaching the boilingpoint. In instances where the aqueous suspension has a temperature ofapproximately 50°-90° C., then mild agitation over a period of about10-60 minutes is satisfactory. Often longer or shorter periods of mildto vigorous agitation may be employed such as from about 1-5 minutes toseveral hours at temperatures varying, respectively, between the boilingpoint and the freezing point. When desired, the agitation may becontinued long after the catalyst-containing micelles are formed ascontinued agitation does not seem to have an adverse affect.

As a general rule, the micelle-forming surfactants known in the priorart may be used in practicing the present invention. Micelle-formingsurfactants used in the emulsion polymerization of monomeric organiccompounds are disclosed in the text Synthetic Rubber, by G. S. Whitby,et al, John Wiley & Sons Incorporated, New York (1954), and surfaceactive agents in general are disclosed on pages 418-424 of the textOrganic Chemistry, Fieser and Fieser, 2nd Edition, Reinhold PublishingCorporation, New York, New York (1950), the disclosures of which areincorporated herein by reference. Examples of surfactants disclosed inthe above tests include the alkali metal soaps of long chain fattyacids, and expecially the sodium and potassium soaps of fatty acidscontaining about 14-25 carbon atoms and preferably about 16-18 carbonatoms, and the sodium and potassium soaps of the rosin acids, abieticacid and the derivatives thereof. Other micelle-forming surfactantsinclude fats and oils such as corn oil, cotton seed oil, castor oil, soybean oil and safflower oil which have been fully or partially saponifiedwith alkali metal bases to produce mixtures including saponified longchain fatty acids, the mono- or di-glycerides thereof, and glycerin.

Examples of synthetic micelle-forming surfactants include the sulfonatesof long chain alcohols prepared by hydrogenation of naturally ocurringfats and oils of the above types and especially sulfonated long chainalcohols containing about 10-20 and preferably about 12-14 carbon atoms,the alkali metal salts of the monosulfonates of monoglycerides such assodium glyceryl monolaurate sulfonate, the sulfonates of succinic acidesters such as dioctyl sodium sulfosuccinate and the alkylaryl alkalimetal sulfonates. Specific examples of presently preferredmicelle-forming surfactants include sodium and potassiumsulforicinoleate, tetrahydronaphthalene sulfonate, octahydroanthracenesulfonic acid, butyl naphthalene sulfonic acid, sodium xylene sulfonate,alkyl benzene sulfonic acid and potassium benzene sulfonate.

Sulfated long chain hydroxycarboxylic acids containing about 14-25carbon atoms and preferably about 16-18 carbon atoms, and sulfated fatsand oils containing hydroxycarboxylic acids of this type produceexceptionally good micelle-forming surfactants. At least 25% of thehydroxyl groups and preferably at least 50% should be sulfated, and upto 95-100% may be sulfated. It is usually preferred that the sulfatedoils and/or long chain hydroxycarboxylic acids be neutralized with analkali metal base, and that the corresponding alkali metal salts beadded to the colloidal suspension in the form of an aqueous solution.The aqueous solution may contain at least 25% of water and preferably atleast 35-40% by weight. Much larger percentages of water may be presentwhen desired such as 75-80% or more by weight.

A very active catalyst is produced when using sulfated castor oil as themicelle-forming surfactant (Turkey Red oil). Sulfated castor oil whichhas been purified sufficiently to be of U.S.P. or medicinal gradeproduces an exceptionally active catalyst. For the best results, thecastor oil is reacted with about an equal weight of concentratedsulfuric acid (e.g., 20% by weight) at a temperature of approximately25°-30° C. The mixture may be reacted for about two hours with stirringand is then neutralized with sodium hydroxide solution. The reactionmixture separates into three layers, i.e., an upper layer which is awater solution, an intermediate or oily layer, and a white curdyprecipitate. The intermediate oily layer is separated from the upper andlower layers, and may be added to the colloidal suspension as themicelle-forming surfactant in an amount, for example, of 0.001-0.1 moleper liter, and preferably about 0.005 mole per liter.

The activity of the catalyst may be increased very markedly by coolingthe aqueous catalyst suspension to a temperature approaching thefreezing point such as about 0°-10° C., and then warming over one ormore cycles. For best results, the aqueous catalyst suspension should befrozen and thewed over one or more cycles. The reason for the increasedcatatylic activity is not fully understood at the present time butcooling and then warming the aqueous catalyst suspension seems toincrease the concentration of the catalyst-containing micelles and/orincreases the catalytic activity thereof.

The aqueous suspension of the catalyst contains a relatively smallpercentage by weight of the active catalyst as produced. When desired,it may be concentrated by evaporating a portion of the water to producea concentrated liquid catalyst suspension which may be stored and usedmore conveniently. It is also possible to prepare a dry catalystconcentrate by evaporating substantially all of the water. The preferredmethod of producing the dry catalyst concentrate is by flash evaporationusing a technique analogous to that employed in preparing powdered milk.The catalyst concentrates produced upon partial or complete evaporationof the water content of the initially prepared aqueous suspension may bereconstituted by addition of water with little or no loss of catalyticactivity. Preferably, the water is added to the dry catalyst concentrateunder sufficiently vigorous conditions of agitation to assure that thecatalyst micelles are resuspended and uniformly distributed.

The aqueous catalyst suspension may be used as produced for treating thecoal, lignite and peat, or it may be diluted with approximately 2-10,000parts by weight of water. For better results, the catalyst suspension asproduced may be diluted with about 250-2,000 parts by weight of water,and preferably with about 500-1,000 parts by weight of water, and thenused. It is only necessary that the coal, lignite and peat be treatedwith a liquid phase aqueous medium containing a catalytic amount of thecatalyst. The aqueous medium may contain, for example, about 0.0001-0.3%by weight of the catalyst, but larger or smaller amounts may be presentwhen desired. Usually the aqueous medium contains about 0.004-0.08% byweight of the catalyst, and often about 0.006-0.007% by weight gives thebest results. A surface active agent may be added thereto when desiredas previously discussed. Alternatively the dry catalyst or liquidcatalyst concentrate may be admixed with water and/or the surface activeagent to provide an effective catalyst concentration in the quantitiespreviously discussed. The weight of the catalyst is calculated on a drysolids basis, i.e., the weight of the catalyst ingredients in theaqueous suspension as produced after removal of the water.

In a further variant of the process for preparing the catalyst, at leastone dissolved substance providing at least one amphotericmetal-containing ion is present in the aqueous medium at the time ofreacting the alkali metal silicate with the substances providing calciumion and magnesium ion. The substance or substances providing theamphoteric metal-containing ion or ions may be present, for example, inan amount sufficient to provide about 0.0001-1% and preferably about0.01-0.5% by weight when calculated as the amphoteric metal oxide andbased upon the weight of the alkali metal silicate. Preferred amphotericmetals include aluminum and/or zinc, and the preferred sources thereofinclude alkali metal aluminate and zincate of which sodium aluminateand/or zincate usually give the best results. The alkali metal aluminateand/or zincate may be added directly to the aqueous medium, or as themineral acid salts, oxides and/or hydroxides which then form the alkalimetal aluminate and/or zincate under the highly alkaline conditions thatexist.

Surprisingly, an aqueous suspension of catalyst which was usedpreviously in treating coal, lignite and peat in the process of theinvention produces a more active catalyst than either distilled water ordeionized water. In one preferred variant of the invention, spentaqueous catalyst suspension is recycled indefinitely in a process fortreating the coal, lignite or peat with periodic additions of thechemicals necessary to maintain the desired concentration of thecatylyst. The catalyst produced by this variant exhibits greatlyenhanced initial catalytic activity and results in a rapid attack on theactive sites of the coal, lignite and peat.

The invention is further illustrated by the following specific examples.

EXAMPLE I

This example illustrates one presently preferred process for preparingthe novel catalyst used in practicing the invention.

Anhydrous calcium chloride in an amount of 0.66 gram and magnesiumsulfate heptahydrate in an amount of 1.32 grams were dissolved in twoliters of deionized water with stirring and warming until solution wascomplete. Then 95 grams of sodium silicate pentahydrate having amolecular ratio of sodium oxide to silicon dioxide of 1:1 were added tothe solution with stirring and continued warming to produce a whitecollodial suspension of the reaction product.

After setting for 10 minutes, the colloidal suspension was heated to 80°C. and sulfated castor oil in an amount of 201 grams was added withstirring. The average molecular weight of the sulfated castor oil was940 and it contained 50% of water. The turbidity lessened somewhat asthe colloidal suspension was heated at 80°-90° C. for one hour withvigorous stirring to produce catalyst micelles. The aqueous suspensionof catalyst micelles thus prepared had a viscosity similar to that ofwater and it was used as the catalyst in certain Examples as notedhereinafter.

A dry or solid catalyst concentrate was prepared in a further run byevaporating water from the initially prepared aqueous catalystsuspension. The resulting dry catalyst concentrate was resuspended inwater and there was no substantial loss of catalytic activity. In stillother runs, the catalytic activity of the aqueous suspension of catalystas initially prepared, the diluted aqueous suspension of catalyst, andthe reconstituted aqueous catalyst suspension was enhanced by freezingand thawing.

EXAMPLE II.

This example illustrates the preparation of additional catalystsuspensions.

Five suspensions of the catalyst were prepared for the same ingredientsas used in Example I and following the general procedure of Example I.The ratios of ingredients were varied as follows:

    ______________________________________                                                   Amount of Ingredient                                               Ingredient   Run 1   Run 2   Run 3 Run 4 Run 5                                ______________________________________                                        Deionized water                                                                            2 l     1.5 l   1.5 l 1.5 l 0.25 l                               CaCl.sub.2   0.66 g  0.5 g   0.5 g 1.0 g 0.5 g                                MgSO.sub.4 . 7H.sub.2 O                                                                    1.32 g  1.0 g   1.0 g 2.0 g 1.0 g                                Na.sub.2 SiO.sub.3 . 5H.sub.2 O                                                            165 g   132 g   71 g  185 g 71 g                                 Sulfated Castor                                                                            100 ml  150 ml  150 ml                                                                              200 ml                                                                              150 ml                               oil (approximately                                                            50% by weight H.sub.2 O)                                                      ______________________________________                                    

The catalyst suspensions prepared by the above five runs used in certainexamples as noted hereinafter.

EXAMPLE III

A portion of a concentrated suspension of catalyst prepared inaccordance with Example I was diluted with 100 volumes of water. Theresulting diluted catalyst suspension was used in treating small lumpsof sub-bituminous coal in a ball mill.

The lumps of coal and the diluted catalyst suspension were fed to theball mill at ambient temperature in the proportion of one pound of coalto one pound of catalyst suspension. The ball mill was rotated for 12hours. Under these conditions, the coal lost its crystalline appearanceand acquired the physical appearance and properties of weathered(oxidized) lignite or Leonardite.

Samples of the treated and untreated coal having about the same particlesize were extracted with aqueous acetic acid and then wtih aqueoussodium hydroxide solution. The solubility of the treated coal wasmarkedly greater than that of the original coal. It was apparent thattreating the coal with the catalyst suspension changed the chemicalcomposition and/or altered the bonds therein to produce both acidsoluble and alkali soluble chemicals.

A portion of the treated coal was exposed to air for 1 hour at 100° C.The initial oxidation was carried further, and a mixture of watersoluble acidic compounds such as phenols, carboxylic acids, andhydroxycarboxylic acids, was produced and subsequently extracted withaqueous sodium hydroxide solution. The degree of oxidation achieved bythis treatment was equivalent to oxidizing the coal at 150° C. for aperiod of eight hours in shallow pans with frequent stirring. Treatingcoal with the aqueous catalyst suspension not only resulted in aremarkable degree of oxidation, but also seemed to activate theoxidizable sites whereby it was further oxidized by exposure to air in aminimum period of time and at low temperature.

A substantial amount of gas was liberated in the ball mill whiletreating the coal and a significant pressure was built up. The off gasescontained hydrogen cyanide, cyanogen, hydrogen sulfide, sulfure dioxide,sulfure trixoide and carbon dioxide. The composition of the off gasesindicated that the action of the catalyst suspension on the coal was oneof oxidation.

A second portion of coal treated in the ball mill was extracted withacetone and then with benzene. Upon evaporating the solvents, a mixtureof organic chemicals was obtained in each instance and it was notpossible to determine the exact chemical composition. However, thecompounds were different from those obtained upon extracting the treatedcoal with aqueous acetic acid and aqueous sodium hydroxide.

A third sample of the treated coal was analyzed. The treated coalcontained substantially no alkali metal compounds or combustible sulfurand nitrogen compounds. The heating value was not changed significantlyand the treated coal is a low sulfur and low nitrogen containing fuelwhich may be burned in coal burning furnaces. Upon combustion, thetreated coal produces very little air pollution due to sulfur andnitrogen oxides and tube failure in furnaces is reduced to a minimum.

EXAMPLE IV

The five catalyst suspensions prepared by the five runs of Example IIwere tested for catalytic activity following the general procedure ofExample III and were rated as active catalysts.

A portion of the catalyst suspension from each of the runs was frozenand thawed. When tested in accordance with the procedure of Example III,the frozen and thawed catalyst suspension had an even higher catalyticactivity.

A portion of the frozen and thawed catalyst suspension from Run 4 ofExample II was evaporated to dryness and the dry residue was used toprepare an aqueous catalyst suspension in deionized water. The catalystsuspension contained 1 part of the dry residue for each 600 parts ofdeionized water and it was an effective catalyst when tested inaccordance with the procedure of Example III.

EXAMPLE V

This Example illustrates a further presently preferred process forpreparing the catalyst of the invention.

Anhydrous calcium chloride in an amount of 0.66 gram and magnsiumsulfate heptahydrate in an amount of 1.32 grams were dissolved in oneliter of soft water heated to 80° C. Then 95 grams of sodium silicatepentahydrate was added to the resulting solution with stirring toproduce a suspension of finely divided particles of the reactionproduct. The sodium silicate pentahydrate contained approximately 0.12gram of aluminum when calculated as Al₂ O₃ and a somewhat smaller amountof zinc when calculated as ZnO.

The suspension of the reaction product was maintained at 80° C. andstirred for one-half hour. Then an aqueous solution prepared by admixing75 grams of sulfated castor oil with 100 mililiters of water was addedslowly with stirring. The stirring was continued for one-half hourthereafter while maintaining the reaction mixture at 80° C. to producecatalyst-containing micelles.

The sulfated castor oil contained 6.5-7% of organically combined SO₃ ona dry basis, 0.9-1.1% of combined alkali when calculated as sodiumoxide, no free alkali, and 50% ± 1% of material volatile at 105° C.which was mostly water. The average molecular weight of the sulfatedcastor oil molecule was approximately 400 grams per mole.

The above prepared suspension of catalyst was placed in plasticcontainers awaiting testing and use. The catalyst suspension was testedin accordance with Example III and was rated as a superior catalyst. Itwas possible to add from 1,000 to 10,000 parts of water to a portion ofthe catalyst suspension and still obtain excellent catalytic acitivity.

A further portion of the catalyst suspension was frozen and thawed, andthen tested in accordance with the procedure of Example III. The coolingand warming steps enhanced the catalytic activity.

A further portion of the catalyst suspension was admixed withcommercially available surfactants in quantities sufficient to serve asa laundry detergent. No detrimental effects were noted. It was alsopossible to add additional alkali metal silicate having a mole ratio ofSiO₂ to Na₂ O of 1.6:1 to 3:1 without detrimental effects. Thus, theaqueous catalyst suspension is sufficiently stable to allow addition oflaundry detergents or builders such as alkali metal silicates,nitrilotriacetic acid and phosphates.

EXAMPLE VI

The general procedure of Example V was followed with the exception ofusing 0.33 gram of anhydrous calcium chloride rather than 0.66 gram,0.66 gram of magnesium sulfate heptahydrate rather than 1.32 grams, and45 grams of sodium silicate pentahydrate rather than 95 grams. Theremaining ingredients and steps in the Example I procedure for preparingthe catalyst were not changed.

The resulting catalyst suspension was approximately one-half asconcentrated as that prepared in Example V. Upon testing in accordancewith Example III, it was found to be as effective as the catalyst ofExample V when calculated on a dry solid basis. It was also possible toadd surfactants and alkali metal silicates as described in Example Vwithout adverse effect. Cooling the catalyst suspension to temperaturesapproaching the freezing point or freezing, followed by warming orthawing, also had a beneficial effect upon the catalytic activity.

EXAMPLE VII

This Example illustrates the preparation of the fossil fuel solutions ofthe invention from lignite.

Lignite from the Havelock Mine, New England, North Dakota was ground tominus 60 mesh (Tyler Screen) and 200 grams thereof was admixed with 250ml of a catalyst suspension prepared in accordance with Example I anddiluted with 1000 volumes of water. The admixture was treated for 2hours at room temperature (72° F.) in a 1 quart Abbe Ball Mill using 3/4inch ceramic balls. Following the treatment, the reaction mixture wasfiltered to obtain a glassy black pitch-like solid residue of treatedlignite particles and a yellow liquid treating solution having a pH of6.7

The treated lignite particles were extracted with acetone to produce adark red solution and a residue of acetone extracted particles. Theacetone extracted particles were further extracted with 3 M hydrochloricacid to obtain a yellow-orange acidic extract solution and an acidextracted residue.

The acid extracted char was further treated with 1 M sodium hydroxidesolution and the mixture set to a jet-black pitchlike substance. Thesolution was filtered with difficulty to yield a black thick liquid anda sodium hydroxide treated residue. When the residue was washed withwater, the solid material peptized and passed through the filter. Thus,substantially all of the lignite was solubilized.

EXAMPLE VIII

This Example illustrates the preparation of an aqueous solution ofcatalyst treated lignite.

Weathered lignite having a particle size of minus 80 mesh (Tyler Screen)was admixed in an amount of 50 pounds with 2.50 ml of the catalystsuspension prepared in accordance with Example I and 8 gallons of hotsoft water having a temperature of 150° F. The admixture was heated andstirred and after five minutes, the pH value was approximately 5. Theadmixture was allowed to set without heating for 12 hours and then 2pounds of flake caustic (78% sodium hydroxide) was added. The admixturewas stirred for approximately 5 minutes and the pH was 5-6. The wetcatalyst treated lignite was air dried and stored in a plasticcontainer.

The above prepared catalyst treated lignite was admixed in an amount of298 grams with 307 grams of the catalyst suspension prepared inaccordance with Example I. The resultant moist solid was stored in anairtight container while awaiting the preparation of a solution.Thereafter, 5 grams of this admixture was added to one gallon of softwater. Substantially all of the treated lignite dissolved forming a darkopaque blue-black solution. The solution contained the catalyst in aconcentration equivalent to diluting the catalyst suspension of ExampleI with 1000 volumes of water and it also contained 700 parts per millionof the dissolved catalyst treated lignite. The pH value was 7.

The above prepared lignite solution was tested on cultures ofStaphylococcus Aures (gram positive) and Escherichia Coli (gramnegative). The solution completely inhibited the growth of bothStaphylococcus Aures and Escherichia Coli.

EXAMPLE XI

This Example illustrates the treatment of Havelock Mine lignite having aparticle size such that 85% passed through a minus 85 mesh Tyler Screen.

An admixture of 70 pounds of the lignite, 300 ml of the catalystsuspension prepared in accordance with Example I and 8 gallons of softwater having a temperature of 150° F. was prepared. After 5 minutes ofheating and stirring, the pH was 5 and 2.2 pounds of flake caustic soda(78% sodium hydroxide) was added. The pH of the resultant solution was12 and after one-half hour of heating the pH was 11. The admixture wasallowed to set for 12 hours.

Thereafter 1/2 of the treated lignite was air dried. A whiteencrustation appeared on the surface after drying. A second 1/2 portionof the treated lignite was kept moist with water for 2 days to determineif air oxidation continues provided the treated lignite is kept moistand basic. Upon testing, it was found that the air oxidation didcontinue. A white encrustation formed on the surface of the treatedlignite when dry. The remaining 1/3 portion of the treated lignite wasadmixed with 2 gallons of hot soft water and thereafter 100 grams ofsodium perborate was added. The temperature was 76° C. Thereafter, thetreated lignite was air dried in the sun and no white encrustationdeveloped on the surface.

I claim:
 1. A process for treating solid fossil fuel with an aqueousmedium comprisingintimately contacting solid fossil fuel in particulateform selected from the group consisting of coal, lignite, peat andadmixtures thereof with an aqueous medium containing a catalyticallyeffective amount of a catalyst, the solid fossil fuel having activesites therein which react with at least one component of the aqueousmedium under liquid phase conditions in the presence of the catalyst,the particles of the solid fossil fuel being intimately contacted withthe aqueous medium under liquid phase conditions until active sitesthereof react with at least one component of the aqueous medium, thecatalyst being prepared by a process comprisingadmixing a water solublealkali metal silicate with an aqueous medium containing a dissolvedsubstance which is a source of calcium ion and a dissolved substancewhich is a source of magnesium ion, the aqueous medium containing saiddissolved substances in amounts to provide between about 1 × 10⁻⁴ and 1× 10⁻¹ mole per liter each of calcium ion and magnesium ion, the aqueousmedium containing said dissolved substances in amounts to provide amolar ratio of calcium ion to magnesium ion between about 2.0:1.0 and1.0:2.0; the alkali metal silicate having an alkali metal oxide tosilicon dioxide ratio between about 0.9:1.0 and less than 2.0:1.0 andbeing admixed with the aqueous medium in an amount of about 0.05-2 molesper liter, reacting the alkali metal silicate with said dissolvedsubstances providing calcium ion and magnesium ion to produce an aqueoussuspension of finely divided particles of the reaction product, admixinga micelle-forming surfactant with the aqueous medium in an amount toform catalyst micelles comprising said finely divided particles uponagitating the aqueous medium, and agitating the aqueous mediumcontaining the finely divided particles and surfactant to form saidcatalyst micelles.
 2. The treated solid fossil fuel prepared by theprocess of claim
 1. 3. The process of claim 1 wherein the solid fossilfuel is coal.
 4. The process of claim 1 wherein the solid fossil fuel islignite.
 5. The process of claim 1 wherein the solid fossil fuel ispeat.
 6. The process of claim 1 wherein in the process for preparing thecatalyst, said ratio of calcium ion to magnesium ion is between about1.5:1.0 and 1.0:1.5.
 7. The process of claim 1 wherein in the processfor preparing the catalyst, said ratio of calcium ion to magnesium ionis about 1.0:1.0.
 8. The process of claim 1 wherein in the process forpreparing the catalyst, the alkali metal silicate is admixed with anaqueous medium containing said dissolved substances in amounts toprovide between about 1 × 10⁻³ and 6 × 10⁻³ mole per liter each ofcalcium ion and magnesium ion.
 9. The process of claim 1 wherein in theprocess for preparing the catalyst, the alkali metal silicate is admixedwith an aqueous medium containing said dissolved substances in amountsto provide between about 2.5 × 10⁻³ and 3.0 × 10⁻³ mole per liter eachof calcium ion and magnesium ion.
 10. The process of claim 1 wherein inthe process for preparing the catalyst, about 0.2-0.3 mole per liter ofthe alkali metal silicate is admixed with the aqueous medium.
 11. Theprocess of claim 1 wherein in the process for preparing the catalyst,the alkali metal silicate has an alkali metal oxide to silicon dioxideratio between about 0.9:1.0 and 1.2:1.0.
 12. The process of claim 1wherein in the process for preparing the catalyst, the alkali metalsilicate is alkali metal metasilicate having an alkali metal oxide tosilicon dioxide ratio of about 1.0:1.0.
 13. The process of claim 1wherein in the process for preparing the catalyst, about 0.001-0.1 moleper liter of the surfactant is admixed with the aqueous medium.
 14. Theprocess of claim 1 wherein in the process for preparing the catalyst,the surfactant comprises sulfated castor oil.
 15. The process of claim 1wherein in the process for preparing the catalyst, the alkali metalsilicate is admixed with an aqueous medium containing said dissolvedsubstances in amounts to provide between about 1 × 10⁻³ and 6 × 10⁻³mole per liter each of calcium ion and magnesium ion, the ratio ofcalcium ion to magnesium ion is between about 1.5:1.0 and 1.0:1.5, about0.1-1 mole per liter of the alkali metal silicate is admixed with theaqueous medium, and the alkali metal silicate has an alkali metal oxideto silicon dioxide ratio between about 0.9:1.0 and 1.2:1.0.
 16. Theprocess of claim 1 wherein in the process for preparing the catalyst,the alkali metal silicate is admixed with an aqueous medium containingsaid dissolved substances in amounts to provide between about 2.5 × 10⁻³and 3.0 × 10⁻³ mole per liter each of calcium ion and magnesium ion, theaqueous medium contains about equimolar amounts of calcium ion andmagnesium ion, about 0.2-0.3 mole per liter of the alkali metal silicateis admixed with the aqueous medium, and the akali metal silicate has analkali metal oxide to silicon dioxide ratio of about 1.0:1.0.
 17. Theprocess of claim 16 wherein in the process for preparing the catalyst,the alkali metal metasilicate is sodium metasilicate having an alkalimetal oxide to silicon dioxide ratio of about 1.0:1.0
 18. The process ofclaim 16 wherein in the process for preparing the catalyst, about0.03-0.07 mole per liter of the surfactant is admixed with the aqueousmedium.
 19. The process of claim 18 wherein in the process for preparingthe catalyst, the surfactant comprises sulfated castor oil.
 20. Theprocess of claim 19 wherein in the process for preparing the catalyst,the alkali metal metasilicate is sodium metasilicate having a sodiumoxide to silicon dioxide ratio of about 1.0:1.0.
 21. The process ofclaim 20 wherein in the process for preparing the catalyst, at least 25%of the hydroxy groups of the castor oil are sulfated, and about 0.03-0.07 mole per liter of the sulfated castor oil is admixed with theaqueous medium.
 22. The process of claim 16 wherein in the process forpreparing the catalyst, the alkali metal silicate is admixed with anaqueous medium containing said dissolved substances in amounts toprovide about 2.9 × 10⁻³ mole per liter of calcium ion and about 2.7 ×10⁻³ mole per liter of magnesium ion, about 0.25 mole per liter ofsodium metasilicate having a sodium oxide to silicon dioxide ratio ofabout 1.0:1.0 is admixed with the aqueous medium, the aqueous mediumcontains not more than 10 parts per million by weight of carbonate ionand bicarbonate ion, the surfactant comprises sulfated castor oil and atleast 50% of the hydroxy groups of the castor oil are sulfated, andabout 0.05 mole per liter of the sulfated castor oil is admixed with theaqueous medium.
 23. The process of claim 1 wherein the fossil fuel istreated with an oxidizing agent before, during or following treatmentwith the said aqueous medium containing the catalyst to thereby aid insolubilizing additional organic compounds.
 24. The process of claim 1wherein the said particles of the solid fossil fuel are intimatelycontacted with the aqueous medium until active sites thereof areoxidized, and the said particles of the fossil fuel are treated in avessel constructed from an electrically conductive metal to therebycontrol the degree of oxidation.
 25. The process of claim 1 wherein thesaid particles of the solid fossil fuel are intimately contacted withthe aqueous medium until active sites thereof are oxidized, and the saidparticles of the fossil fuel are treated in a vessel which is an organicnon-conductor of electricity to thereby control the degree of oxidation.26. The process of claim 1 wherein the said particles of the solidfossil fuel are intimately contacted with the aqueous medium untilactive sites thereof are oxidized, and the said particles of the fossilfuel are treated in a glass or ceramic vessel to thereby control thedegree of oxidation.
 27. The process of claim 1 wherein subsequent totreating the said particles of the fossil fuel with the catalystcontaining aqueous medium, the aqueous medium is evaporated whereby thecatalyst content thereof is deposited on the treated particles of thefossil fuel.
 28. The catalyst containing particles of treated fossilfuel prepared by the process of claim 27.